EP0576362A2 - Thermally stable und chemically resistant glasses - Google Patents
Thermally stable und chemically resistant glasses Download PDFInfo
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- EP0576362A2 EP0576362A2 EP93401624A EP93401624A EP0576362A2 EP 0576362 A2 EP0576362 A2 EP 0576362A2 EP 93401624 A EP93401624 A EP 93401624A EP 93401624 A EP93401624 A EP 93401624A EP 0576362 A2 EP0576362 A2 EP 0576362A2
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- glass
- glasses
- glass composition
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
Definitions
- the present invention relates to glass compositions which have both a lower high annealing temperature, a low coefficient of expansion and good chemical resistance.
- the glasses according to the invention are advantageous for all applications requiring such properties.
- the glasses according to the invention are also capable of being transformed into sheets which, cut to the desired format, possibly polished or treated, will serve as elements for the production of fire-resistant glazing or substrates on which will be deposited electrically layers active. These substrates thus coated with layers are generally called slabs in the electronic industry. These tiles are combined to form display screens such as liquid crystal, plasma or electroluminescent screens.
- Glasses known for their great physical stability during a rise in temperature, combined with good chemical resistance, are numerous and generally belong to the large family of borosilicate glasses, in particular alumino-borosilicate glasses comprising alkaline earth oxides.
- the glasses, transformed into sheets and then cut to later serve as substrates, are selected in particular according to the physicochemical properties that these the latter must possess.
- the deposition of electrically active layers on a glass substrate is obtained after several operations during which the glass has been subjected to relatively high temperatures.
- the glass must not deform during these operations and therefore have the lowest possible strain point temperature.
- the coefficient of thermal expansion of the glass forming the substrate must be compatible with that of the layers which are deposited on its surface.
- the glass must practically not contain elements liable to migrate into the layers formed and to deteriorate their properties; this is the case, in particular, for alkalis.
- These glasses must also have viscosity and devitrification characteristics adapted to the process chosen to obtain a glass sheet whose thickness is the most uniform and the most regular surface possible.
- These glasses must also have good chemical resistance with respect to acidic media, in particular with respect to solutions based on hydrofluoric acid.
- One of the methods that can be used consists in bringing the molten glass into a device the top of the side walls of which converge downwards serves as a weir.
- the glass flows along the side walls, thus forming two streams which meet at the tip of the device, before being stretched vertically from top to bottom in the form of a flat sheet.
- Such a process requires that the glass has, at liquidus temperature, a viscosity equal to at least 2 to 3.105 poises.
- Such glasses are, for example, illustrated by US-A-4,824,808.
- Another method consists in coating the molten glass on a metal tin bath according to the well-known technique of float glass. Glass compositions capable of being floated and intended to serve as substrates for forming flat screens are described in particular in patent application WO 89/02877.
- the subject of the invention is glass compositions capable of being floated, which have the physicochemical characteristics required for fire-resistant glazing or for active matrix screen substrates and which are economically advantageous.
- the invention also relates to glass compositions comprising a limited amount of expensive constituents.
- a subject of the invention is also glass compositions capable of making it possible to obtain packaging which is resistant in particular to thermal shock.
- SiO2 is one of the oxides which form the glass network of the glasses according to the invention and plays an essential role for their stability.
- the cationic percentage of this constituent is less than 46%, the chemical resistance of the glass can only be maintained by increasing the percentage of B2O3, therefore economically undesirable.
- the cationic percentage of silica exceeds 56%, the melting of the vitrifiable mixture becomes difficult and the viscosity of the glass increases, making its refining and its coating on the tin bath difficult.
- B2O3 also plays an essential role for the stability of the glasses according to the invention. This constituent improves the chemical resistance of the glasses according to the invention, it reduces their viscosity at high temperatures as well as the melting temperature of the batch. B2O3 also reduces the ability of the glass to devitrify. Beyond 23%, this influence of B2O3 decreases; in addition, a high content of B3O3 has the effect of reducing the lower annealing temperature. Below 10% the devitrification of the glass increases and its viscosity increases.
- Alumina also plays a stabilizing role. This constituent increases the lower annealing temperature and, to some extent, the chemical resistance of the glass. Below 12% this resistance becomes too weak; above 17%, the glasses are more difficult to melt and their viscosity at high temperatures increases too much; in addition, their chemical resistance undesirably decreases.
- the alkaline earth oxides also play a very important role in the glasses according to the invention: they promote their melting and reduce their viscosity at high temperatures.
- CaO plays an important role. Unlike many constituents whose influence on the viscosity curve is practically reflected by a translation of said curve towards higher or lower temperatures as the case may be, lime, in the context of the invention, has the effect of cause a straightening of the viscosity curve. The difference between the temperatures corresponding to two determined viscosities is smaller for the glasses according to the invention than that presented by an ordinary soda-lime-silica glass.
- This phenomenon has the effect of maintaining or even increasing the lower annealing temperature, of facilitating the melting of the batch and the refining of the glass obtained and of reducing the temperature at which the glass can be coated on the surface of the bath. 'tin.
- a CaO content of the order of 9% is necessary. Above 15%, CaO increases the coefficient of expansion in unacceptable proportions.
- the glasses according to the invention which are relatively rich in CaO are of moderate cost because this constituent comes from inexpensive raw materials. This economic advantage is all the more marked for the glasses which are richest in CaO and whose B2O3 content is reduced.
- the glasses according to the invention systematically include magnesia because this constituent makes it possible to increase the chemical resistance of the glasses and to decrease their coefficient of expansion; it also makes it possible to reduce their viscosity at high temperatures.
- the higher content of MgO is limited to 4% because, beyond this, this oxide accentuates the tendency to devitrification of the glasses according to the invention.
- SrO and possibly BaO contributes to the reduction of the viscosity of the glasses at high temperatures. These oxides also reduce the risk of devitrification.
- SrO has the effect of straightening the viscosity curve, but to a lesser degree than CaO.
- SrO can be introduced up to a content, expressed as a cationic percentage, of the order of 7% without causing an excessive increase in the coefficient of expansion.
- BaO can optionally be introduced into the glasses according to the invention, but according to relatively low contents. Indeed, if this oxide decreases the viscosity, it has no influence on the slope of the viscosity curve, it increases the coefficient of expansion quite appreciably and the raw materials which bring it are expensive.
- the glasses according to the invention can also comprise other constituents in a limited quantity such as TiO2, which has the effect in particular of increasing the chemical resistance.
- the glasses according to the invention comprise very little, if at all, of alkaline oxides.
- the maximum content of alkalis in these glasses is approximately 0.5% expressed as a cationic percentage.
- compositions according to the invention are easily fusible and the glasses obtained have properties making them particularly suitable for floating on a tin bath.
- compositions of the invention are relatively easy to melt and the glasses obtained easy to refine compared to glasses developed for the same application. This results in reduced energy consumption and less rapid wear of the refractories constituting the furnace. of fusion.
- the glasses of the invention generally have a lower annealing temperature greater than 610 ° C, a coefficient of expansion less than 50.10 ⁇ 7 / ° C and good resistance to attack by a hydrofluoric solution.
- Examples 1 to 8 illustrate the glasses according to the invention
- the thermal characteristics, the devitrification and the viscosity of the glasses illustrating the invention were measured according to methods well known to those skilled in the art. Their chemical resistance was assessed by measuring the weight loss suffered by a 15x30x6 millimeter glass plate, polished on both sides, after its stay in an acid solution. This loss is expressed in mg / cm2.
- the resistance to hydrofluoric acid (R HF ) is measured after a stay of 7 hours, at room temperature, in an aqueous solution of hydrofluoric acid and ammonium fluoride. This etching solution is formed from a 50% solution of hydrofluoric acid and a 40% solution of ammonium fluoride mixed in a weight ratio of 1 to 7.
- the glasses according to the invention are produced from vitrifiable raw materials, some of which are natural and which must have as few impurities as possible.
- the preferred glass compositions according to the invention are distinguished by the following characteristics considered alone or in combination: SiO2 + Al2O3 ⁇ 65% 10% ⁇ CaO ⁇ 14% SrO + BaO ⁇ 4% Na2O ⁇ 0.2%
- the glasses according to the invention are obtained in the form of a ribbon of strictly controlled thickness.
- These sheets cut to the desired format, possibly polished and treated, are mounted to form fire-resistant glazing or serve as a substrate for manufacturing slabs.
- the glasses according to the invention characterized by a lower annealing temperature greater than 600 ° C and by a coefficient of expansion less than 50.10 ⁇ 7 ° C give glass sheets suitable for the production of fire-resistant glazing.
- the glasses according to the invention can be covered with layers based in particular on Si, SiO x , indium and tin oxides (ITO) or metals, in order to produce a fine network of transistors in thin films.
- They can also be covered with different layers allowing the production of colored filters; thus, for example, they can be covered with a Cr or NiCr film, which is then etched by photolithography. A tiling of colors (red, green, blue) is then carried out by depositing colors and photolithography. The whole is covered with a layer of polyimide then ITO.
- They can be covered with a series of layers, at least one of which becomes luminescent under the effect of an electric discharge.
- the slabs thus obtained are combined to form display screens such as liquid crystal, plasma or electroluminescent screens.
- the glasses according to the invention make it possible to obtain packaging, such as bottles or baby bottles, the use of which requires good resistance to thermal shock and great chemical inertness with regard to the products which they are likely to contain.
- These packages are obtained by the well-known technique of blowing or pressing a parison in a mold.
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- General Chemical & Material Sciences (AREA)
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Abstract
Description
La présente invention concerne des compositions de verre qui possèdent tout à la fois une température inférieure de recuisson élevée, un faible coefficient de dilatation et une bonne résistance chimique.The present invention relates to glass compositions which have both a lower high annealing temperature, a low coefficient of expansion and good chemical resistance.
Les verres selon l'invention sont intéressants pour toutes les applications requérant de telles propriétés.The glasses according to the invention are advantageous for all applications requiring such properties.
Ainsi, ils sont susceptibles d'être utilisés dans l'industrie de la gobeleterie pour la fabrication de flacons à usage pharmaceutique ou de biberons.Thus, they are likely to be used in the goblet industry for the manufacture of vials for pharmaceutical use or bottles.
Les verres selon l'invention sont également susceptibles d'être transformés en feuilles qui, découpées au format désiré, éventuellement polies ou traitées, vont servir d'éléments pour la réalisation de vitrages anti-feu ou de substrats sur lesquels seront déposées des couches électriquement actives. Ces substrats ainsi revêtus de couches sont généralement appelés dalles dans l'industrie électronique. Ces dalles sont associées pour former des écrans de visualisation tels que les écrans à cristaux liquides, à plasma ou électroluminescents.The glasses according to the invention are also capable of being transformed into sheets which, cut to the desired format, possibly polished or treated, will serve as elements for the production of fire-resistant glazing or substrates on which will be deposited electrically layers active. These substrates thus coated with layers are generally called slabs in the electronic industry. These tiles are combined to form display screens such as liquid crystal, plasma or electroluminescent screens.
Les verres connus pour leur grande stabilité physique lors d'une élévation de température, jointe à une bonne résistance chimique, sont nombreux et appartiennent généralement à la grande famille des verres borosilicatés, en particulier des verres alumino-borosilicatés comprenant des oxydes alcalino-terreux.Glasses known for their great physical stability during a rise in temperature, combined with good chemical resistance, are numerous and generally belong to the large family of borosilicate glasses, in particular alumino-borosilicate glasses comprising alkaline earth oxides.
Les verres, transformés en feuilles puis découpés pour servir ultérieurement de substrats, sont sélectionnés notamment en fonction des propriétés physico-chimiques que ces derniers doivent posséder. En effet, le dépôt de couches électriquement actives sur un substrat de verre est obtenu à l'issue de plusieurs opérations au cours desquelles le verre a été soumis à des températures relativement élevées. Le verre ne doit pas se déformer au cours de ces opérations et donc présenter la température inférieure de recuisson (strain point) la plus élevée possible. De plus, le coefficient de dilatation thermique du verre formant le substrat doit être compatible avec celui des couches qui sont déposées à sa surface. Enfin, le verre ne doit pratiquement pas comporter d'éléments susceptibles de migrer dans les couches formées et de détériorer leurs propriétés ; c'est le cas, en particulier, des alcalins.The glasses, transformed into sheets and then cut to later serve as substrates, are selected in particular according to the physicochemical properties that these the latter must possess. Indeed, the deposition of electrically active layers on a glass substrate is obtained after several operations during which the glass has been subjected to relatively high temperatures. The glass must not deform during these operations and therefore have the lowest possible strain point temperature. In addition, the coefficient of thermal expansion of the glass forming the substrate must be compatible with that of the layers which are deposited on its surface. Finally, the glass must practically not contain elements liable to migrate into the layers formed and to deteriorate their properties; this is the case, in particular, for alkalis.
Ces verres doivent présenter aussi des caractéristiques de viscosité et de dévitrification adaptées au procédé choisi pour obtenir une feuille de verre dont l'épaisseur soit la plus uniforme et la surface la plus régulière possible.These glasses must also have viscosity and devitrification characteristics adapted to the process chosen to obtain a glass sheet whose thickness is the most uniform and the most regular surface possible.
Ces verres doivent également présenter une bonne résistance chimique à l'égard des milieux acides, notamment vis-à-vis de solutions à base d'acide fluorhydrique.These glasses must also have good chemical resistance with respect to acidic media, in particular with respect to solutions based on hydrofluoric acid.
Un des procédés utilisables consiste à amener le verre fondu dans un dispositif dont le sommet des parois latérales, qui convergent vers le bas, sert de déversoir. Le verre s'écoule le long des parois latérales, formant ainsi deux courants qui se réunissent à la pointe du dispositif, avant d'être étirés verticalement de haut en bas sous la forme d'une feuille plane. Un tel procédé exige que le verre présente, à la température du liquidus, une viscosité égale à au moins 2 à 3.10⁵ poises. De tels verres sont, par exemple, illustrés par le brevet US-A-4 824 808.One of the methods that can be used consists in bringing the molten glass into a device the top of the side walls of which converge downwards serves as a weir. The glass flows along the side walls, thus forming two streams which meet at the tip of the device, before being stretched vertically from top to bottom in the form of a flat sheet. Such a process requires that the glass has, at liquidus temperature, a viscosity equal to at least 2 to 3.10⁵ poises. Such glasses are, for example, illustrated by US-A-4,824,808.
Un autre procédé consiste à napper le verre fondu sur un bain d'étain métallique selon la technique bien connue du verre flotté. Des compositions de verre, susceptibles d'être flottées et destinées à servir de substrats pour former des écrans plats, sont notamment décrites dans la demande de brevet WO 89/02877.Another method consists in coating the molten glass on a metal tin bath according to the well-known technique of float glass. Glass compositions capable of being floated and intended to serve as substrates for forming flat screens are described in particular in patent application WO 89/02877.
Ces verres appartiennent à la famille des alumino-borosilicates comprenant une forte teneur en oxydes alcalino-terreux. Si ces verres possèdent de bonnes caractéristiques physico-chimiques eu égard à l'application considérée, leur composition contient un pourcentage élevé d'oxydes onéreux comme B₂O₃, SrO et BaO. De plus, ils sont relativement visqueux pour le procédé de verre flotté si l'on en juge d'après les exemples illustrant cette invention. En effet, la température correspondant à log η = 4 est égale ou supérieure à 1150°C, voire même à 1200°C. A titre de rappel, la température correspondant à la même viscosité pour un verre flotté ordinaire (verre silico-sodo-calcique) est comprise entre 1000 et 1050°C.These glasses belong to the family of alumino-borosilicates comprising a high content of alkaline earth oxides. If these glasses have good physicochemical characteristics with regard to the application considered, their composition contains a high percentage of expensive oxides such as B₂O₃, SrO and BaO. In addition, they are relatively viscous for the float glass process if judged from the examples illustrating this invention. In fact, the temperature corresponding to log η = 4 is equal to or higher than 1150 ° C, or even 1200 ° C. As a reminder, the temperature corresponding to the same viscosity for an ordinary float glass (soda-lime-silica glass) is between 1000 and 1050 ° C.
D'autres verres, susceptibles également d'être formés par la technique du verre flotté, sont décrits, dans la demande de brevet déposée en FRANCE le 2 juillet 1991, sous le numéro 91.08201.Other glasses, also capable of being formed by the float glass technique, are described in the patent application filed in FRANCE on July 2, 1991, under the number 91.08201.
Ces verres se caractérisent notamment par une faible viscosité aux températures élevées (la température de ces verres correspondant à log η = 3,5 est généralement inférieure à 1180°C) et par une vitesse maximale de dévitrification très faible. Cette dernière caractéristique permet d'éviter l'apparition de cristaux pendant le formage du verre malgré des températures de liquidus susceptibles d'atteindre 1230°C.These glasses are characterized in particular by a low viscosity at high temperatures (the temperature of these glasses corresponding to log η = 3.5 is generally less than 1180 ° C.) and by a very low maximum speed of devitrification. This last characteristic makes it possible to avoid the appearance of crystals during the forming of the glass despite liquidus temperatures likely to reach 1230 ° C.
L'invention a pour objet des compositions de verre susceptibles d'être flottées qui présentent les caractéristiques physico-chimiques exigées pour les vitrages anti-feu ou pour les substrats d'écrans à matrice active et qui sont économiquement intéressantes.The subject of the invention is glass compositions capable of being floated, which have the physicochemical characteristics required for fire-resistant glazing or for active matrix screen substrates and which are economically advantageous.
L'invention a notamment pour objet des compositions de verre dépourvues d'oxyde de zinc, qui se nappent à la surface du bain d'étain à des températures particulièrement basses, la température de liquidus de ces verres demeurant inférieure à leur température correspondant à la viscosité caractéristique de log η = 3,5.The subject of the invention is in particular glass compositions devoid of zinc oxide, which become coated on the surface of the tin bath at particularly low temperatures, the liquidus temperature of these glasses remaining below their temperature corresponding to the characteristic viscosity of log η = 3.5.
L'invention a également pour objet des compositions de verre comprenant une quantité limitée de constituants onéreux.The invention also relates to glass compositions comprising a limited amount of expensive constituents.
L'invention a aussi pour objet des compositions de verre susceptibles de permettre l'obtention d'emballages résistant en particulier aux chocs thermiques.A subject of the invention is also glass compositions capable of making it possible to obtain packaging which is resistant in particular to thermal shock.
Ces buts sont atteints grâce à des compositions de verre qui comprennent les constituants suivants dans les limites définies ci-après et exprimées en pourcentages cationiques :
- SiO₂
- 46 à 56 %
- Al₂O₃
- 12 à 17 %
- B₂O₃
- 10 à 23 %
- CaO
- 9 à 15 %
- MgO
- 0,5 à 4 %
- SrO
- 2 à 7 %
- BaO
- 0 à 4 %
- Na₂O + K₂O
- ≦ 0,5 %
- TiO₂
- 0 à 3 %
- If
- 46 to 56%
- Al₂O₃
- 12 to 17%
- WHERE
- 10 to 23%
- CaO
- 9 to 15%
- MgO
- 0.5 to 4%
- SrO
- 2 to 7%
- BaO
- 0 to 4%
- Na₂O + K₂O
- ≦ 0.5%
- TiO₂
- 0 to 3%
SiO₂ est l'un des oxydes qui forment le réseau vitreux des verres selon l'invention et joue un rôle essentiel pour leur stabilité. Dans le contexte de l'invention, lorsque le pourcentage cationique de ce constituant est inférieur à 46 %, la résistance chimique du verre ne peut être maintenue qu'en augmentant le pourcentage de B₂O₃, donc peu souhaitable économiquement parlant. Lorsque le pourcentage cationique de silice dépasse 56 %, la fusion du mélange vitrifiable devient difficile et la viscosité du verre augmente rendant malaisés son affinage et son nappage sur le bain d'étain.SiO₂ is one of the oxides which form the glass network of the glasses according to the invention and plays an essential role for their stability. In the context of the invention, when the cationic percentage of this constituent is less than 46%, the chemical resistance of the glass can only be maintained by increasing the percentage of B₂O₃, therefore economically undesirable. When the cationic percentage of silica exceeds 56%, the melting of the vitrifiable mixture becomes difficult and the viscosity of the glass increases, making its refining and its coating on the tin bath difficult.
B₂O₃ joue également un rôle essentiel pour la stabilité des verres selon l'invention. Ce constituant améliore la résistance chimique des verres selon l'invention, il diminue leur viscosité aux températures élevées ainsi que la température de fusion du mélange vitrifiable. B₂O₃ diminue également l'aptitude du verre à dévitrifier. Au-delà de 23 %, cette influence de B₂O₃ décroît ; de plus, une teneur élevée en B₂O₃ a pour effet de diminuer la température inférieure de recuisson. Au-dessous de 10 % la dévitrification du verre s'accentue et sa viscosité augmente.B₂O₃ also plays an essential role for the stability of the glasses according to the invention. This constituent improves the chemical resistance of the glasses according to the invention, it reduces their viscosity at high temperatures as well as the melting temperature of the batch. B₂O₃ also reduces the ability of the glass to devitrify. Beyond 23%, this influence of B₂O₃ decreases; in addition, a high content of B₃O₃ has the effect of reducing the lower annealing temperature. Below 10% the devitrification of the glass increases and its viscosity increases.
L'alumine joue également un rôle de stabilisant. Ce constituant augmente la température inférieure de recuisson et, dans une certaine mesure, la résistance chimique du verre. Au-dessous de 12 % cette résistance devient trop faible ; au-dessus de 17 %, les verres sont plus difficiles à fondre et leur viscosité aux températures élevées augmente de façon trop importante ; de surcroît, leur résistance chimique diminue de manière indésirable.Alumina also plays a stabilizing role. This constituent increases the lower annealing temperature and, to some extent, the chemical resistance of the glass. Below 12% this resistance becomes too weak; above 17%, the glasses are more difficult to melt and their viscosity at high temperatures increases too much; in addition, their chemical resistance undesirably decreases.
Les oxydes alcalino-terreux jouent également un rôle très important dans les verres selon l'invention : ils favorisent leur fusion et diminuent leur viscosité aux températures élevées.The alkaline earth oxides also play a very important role in the glasses according to the invention: they promote their melting and reduce their viscosity at high temperatures.
Parmi ces oxydes CaO joue un rôle important. Contrairement à de nombreux constituants dont l'influence sur la courbe de viscosité se traduit pratiquement par une translation de ladite courbe vers des températures plus élevées ou plus faibles selon le cas, la chaux, dans le cadre de l'invention, a pour effet de provoquer un redressement de la courbe de viscosité. L'écart séparant les températures correspondant à deux viscosités déterminées est plus faible pour les verres selon l'invention que celui présenté par un verre silico-sodo-calcique ordinaire.Among these oxides CaO plays an important role. Unlike many constituents whose influence on the viscosity curve is practically reflected by a translation of said curve towards higher or lower temperatures as the case may be, lime, in the context of the invention, has the effect of cause a straightening of the viscosity curve. The difference between the temperatures corresponding to two determined viscosities is smaller for the glasses according to the invention than that presented by an ordinary soda-lime-silica glass.
Ce phénomène a pour effet de maintenir, voire d'augmenter la température inférieure de recuisson, de faciliter la fusion du mélange vitrifiable et l'affinage du verre obtenu et de diminuer la température à laquelle le verre peut être nappé à la surface du bain d'étain. Pour obtenir un redressement notable de la courbe de viscosité, une teneur en CaO de l'ordre de 9 % est nécessaire. Au-delà de 15 %, CaO augmente le coefficient de dilatation dans des proportions inacceptables. Autre avantage : les verres selon l'invention relativement riches en CaO sont d'un coût modéré du fait que ce constituant provient de matières premières bon marché. Cet avantage économique est d'autant plus marqué pour les verres les plus riches en CaO et dont la teneur en B₂O₃ est réduite.This phenomenon has the effect of maintaining or even increasing the lower annealing temperature, of facilitating the melting of the batch and the refining of the glass obtained and of reducing the temperature at which the glass can be coated on the surface of the bath. 'tin. To obtain a significant straightening of the viscosity curve, a CaO content of the order of 9% is necessary. Above 15%, CaO increases the coefficient of expansion in unacceptable proportions. Another advantage: the glasses according to the invention which are relatively rich in CaO are of moderate cost because this constituent comes from inexpensive raw materials. This economic advantage is all the more marked for the glasses which are richest in CaO and whose B₂O₃ content is reduced.
Les verres selon l'invention comprennent systématiquement de la magnésie car ce constituant permet d'augmenter la résistance chimique des verres et de diminuer leur coefficient de dilatation ; il permet également, de diminuer leur viscosité aux températures élevées. La teneur supérieure de MgO est limitée à 4 % car, au-delà, cet oxyde accentue la tendance à la dévitrification des verres selon l'invention.The glasses according to the invention systematically include magnesia because this constituent makes it possible to increase the chemical resistance of the glasses and to decrease their coefficient of expansion; it also makes it possible to reduce their viscosity at high temperatures. The higher content of MgO is limited to 4% because, beyond this, this oxide accentuates the tendency to devitrification of the glasses according to the invention.
L'introduction de SrO et éventuellement de BaO contribue à la diminution de la viscosité des verres aux températures élevées. Ces oxydes permettent aussi de réduire les risques de dévitrification.The introduction of SrO and possibly BaO contributes to the reduction of the viscosity of the glasses at high temperatures. These oxides also reduce the risk of devitrification.
Dans le cadre des verres selon l'invention, SrO a pour effet de redresser la courbe de viscosité, mais à un degré moindre que CaO. SrO peut être introduit jusqu'à une teneur, exprimée en pourcentage cationique, de l'ordre de 7 % sans provoquer une augmentation trop importante du coefficient de dilatation. BaO peut être éventuellement introduit dans les verres d'après l'invention, mais selon des teneurs relativement faibles. En effet si cet oxyde diminue la viscosité, il n'a pas d'influence sur la pente de la courbe de viscosité, il augmente assez sensiblement le coefficient de dilatation et les matières premières qui l'amènent sont chères.In the context of the glasses according to the invention, SrO has the effect of straightening the viscosity curve, but to a lesser degree than CaO. SrO can be introduced up to a content, expressed as a cationic percentage, of the order of 7% without causing an excessive increase in the coefficient of expansion. BaO can optionally be introduced into the glasses according to the invention, but according to relatively low contents. Indeed, if this oxide decreases the viscosity, it has no influence on the slope of the viscosity curve, it increases the coefficient of expansion quite appreciably and the raw materials which bring it are expensive.
Les verres selon l'invention peuvent comprendre également d'autres constituants en quantité limitée comme TiO₂, qui a pour effet notamment d'augmenter la résistance chimique.The glasses according to the invention can also comprise other constituents in a limited quantity such as TiO₂, which has the effect in particular of increasing the chemical resistance.
Afin d'éviter le phénomène de migration d'éléments dans la couche recouvrant la surface d'un substrat constitué d'une feuille de verre, les verres selon l'invention comprennent très peu, voire pas du tout, d'oxydes alcalins. La teneur maximale des alcalins dans ces verres est d'environ 0,5 % exprimée en pourcentage cationique.In order to avoid the phenomenon of migration of elements in the layer covering the surface of a substrate consisting of a glass sheet, the glasses according to the invention comprise very little, if at all, of alkaline oxides. The maximum content of alkalis in these glasses is approximately 0.5% expressed as a cationic percentage.
Grâce à l'action conjointe des différents constituants décrite précédemment, les compositions selon l'invention sont facilement fusibles et les verres obtenus possèdent des propriétés les rendant particulièrement aptes au flottage sur un bain d'étain.Thanks to the joint action of the various constituents described above, the compositions according to the invention are easily fusible and the glasses obtained have properties making them particularly suitable for floating on a tin bath.
Ces avantages peuvent être quantifiés en prenant en considération l'écart mesuré entre deux températures correspondant à deux viscosités déterminées telles que log η = 4,5 et log η = 2,5. Cet écart pour un verre silico-sodo-calcique classique est supérieur à 330°C ; le même écart pour les verres selon l'invention est inférieur à 330°C et, pour les compositions préférées, inférieur à 300°C.These advantages can be quantified by taking into consideration the difference measured between two temperatures corresponding to two determined viscosities such as log η = 4.5 and log η = 2.5. This difference for a conventional soda-lime silica glass is greater than 330 ° C; the same difference for the glasses according to the invention is less than 330 ° C and, for the preferred compositions, less than 300 ° C.
Les compositions de l'invention sont relativement faciles à fondre et les verres obtenus faciles à affiner par rapport à des verres mis au point pour la même application. Cela se traduit par une consommation d'énergie réduite et par une usure moins rapide des réfractaires constituant le four de fusion.The compositions of the invention are relatively easy to melt and the glasses obtained easy to refine compared to glasses developed for the same application. This results in reduced energy consumption and less rapid wear of the refractories constituting the furnace. of fusion.
Les verres selon l'invention présentent généralement une température correspondant à log η = 4 qui est égale ou inférieure à environ 1140°C. Cette caractéristique est importante dans la mesure où la pression de vapeur saturante de l'étain devient non négligeable à partir de 1200°C et croît rapidement à des températures plus élevées. Enfin, les verres selon l'invention présentent une température correspondant à log η = 3,5 qui est supérieure à leur température de liquidus. Cela permet d'écarter les risques de dévitrification pendant le formage du verre.The glasses according to the invention generally have a temperature corresponding to log η = 4 which is equal to or less than about 1140 ° C. This characteristic is important insofar as the saturated vapor pressure of the tin becomes significant from 1200 ° C. and increases rapidly at higher temperatures. Finally, the glasses according to the invention have a temperature corresponding to log η = 3.5 which is higher than their liquidus temperature. This eliminates the risk of devitrification during the forming of the glass.
Les verres de l'invention présentent généralement une température inférieure de recuisson supérieure à 610°C, un coefficient de dilatation inférieur à 50.10⁻⁷/°C et une bonne résistance à l'attaque d'une solution fluorhydrique.The glasses of the invention generally have a lower annealing temperature greater than 610 ° C, a coefficient of expansion less than 50.10⁻⁷ / ° C and good resistance to attack by a hydrofluoric solution.
Les avantages présentés par les verres selon l'invention seront mieux appréciés à travers les quelques exemples figurant dans le tableau en annexe.The advantages presented by the glasses according to the invention will be better appreciated through the few examples appearing in the table in the appendix.
Les exemples 1 à 8 illustrent les verres selon l'invention ; l'exemple 9 est un contre-exemple montrant l'influence de la teneur en CaO sur l'écart séparant les températures correspondant à log η = 4,5 et log η = 2,5.Examples 1 to 8 illustrate the glasses according to the invention; Example 9 is a counterexample showing the influence of the CaO content on the difference separating the temperatures corresponding to log η = 4.5 and log η = 2.5.
Les caractéristiques thermiques, la dévitrification et la viscosité des verres illustrant l'invention ont été mesurées selon les méthodes bien connues de l'homme de l'art. Leur résistance chimique a été appréciée en mesurant la perte de poids subie par une plaquette de verre de 15x30x6 millimètres, polie sur les deux faces, après son séjour dans une solution acide. Cette perte est exprimée en mg/cm². La résistance à l'acide fluorhydrique (RHF) est mesurée après un séjour de 7 heures, à température ambiante, dans une solution aqueuse d'acide fluorhydrique et de fluorure d'ammonium. Cette solution d'attaque est formée d'une solution à 50 % d'acide fluorhydrique et d'une solution à 40 % de fluorure d'ammonium mélangées dans un rapport pondéral de 1 à 7.The thermal characteristics, the devitrification and the viscosity of the glasses illustrating the invention were measured according to methods well known to those skilled in the art. Their chemical resistance was assessed by measuring the weight loss suffered by a 15x30x6 millimeter glass plate, polished on both sides, after its stay in an acid solution. This loss is expressed in mg / cm². The resistance to hydrofluoric acid (R HF ) is measured after a stay of 7 hours, at room temperature, in an aqueous solution of hydrofluoric acid and ammonium fluoride. This etching solution is formed from a 50% solution of hydrofluoric acid and a 40% solution of ammonium fluoride mixed in a weight ratio of 1 to 7.
Les verres selon l'invention sont élaborés à partir de matières premières vitrifiables, dont certaines sont naturelles et qui doivent présenter le moins d'impuretés possible.The glasses according to the invention are produced from vitrifiable raw materials, some of which are natural and which must have as few impurities as possible.
Les compositions de verre préférées selon l'invention, se distinguent par les caractéristiques suivantes considérées seules ou en combinaison :
SiO₂ + Al₂O₃ ≦ 65 %
10 % < CaO ≦ 14 %
SrO + BaO ≦ 4 %
Na₂O < 0,2 %The preferred glass compositions according to the invention are distinguished by the following characteristics considered alone or in combination:
SiO₂ + Al₂O₃ ≦ 65%
10% <CaO ≦ 14%
SrO + BaO ≦ 4%
Na₂O <0.2%
Par la technique du verre flotté, les verres selon l'invention sont obtenus sous la forme d'un ruban d'épaisseur strictement contrôlée.By the float glass technique, the glasses according to the invention are obtained in the form of a ribbon of strictly controlled thickness.
Ces feuilles découpées au format désiré, éventuellement polies et traitées, sont montées pour former des vitrages anti-feu ou servir de substrat pour fabriquer des dalles.These sheets cut to the desired format, possibly polished and treated, are mounted to form fire-resistant glazing or serve as a substrate for manufacturing slabs.
Les verres selon l'invention se caractérisant par une température inférieure de recuisson supérieure à 600°C et par un coefficient de dilation inférieur à 50.10⁻⁷°C donnent des feuilles de verre convenant à la réalisation de vitrages anti-feu. Sous forme de substrat, les verres selon l'invention peuvent être recouverts de couches à base notamment de Si, SiOx, d'oxydes d'indium et d'étain (ITO) ou de métaux, afin de réaliser un fin réseau de transistors en films minces.The glasses according to the invention, characterized by a lower annealing temperature greater than 600 ° C and by a coefficient of expansion less than 50.10⁻⁷ ° C give glass sheets suitable for the production of fire-resistant glazing. In the form of a substrate, the glasses according to the invention can be covered with layers based in particular on Si, SiO x , indium and tin oxides (ITO) or metals, in order to produce a fine network of transistors in thin films.
Ils peuvent être également recouverts de différentes couches permettant la réalisation de filtres colorés ; ainsi, par exemple, ils peuvent être recouvert d'un film de Cr ou NiCr, qui est ensuite gravé par photolithographie. Un pavage de couleurs (rouge, vert, bleu) est ensuite réalisé par dépôt de couleurs et photolithogravure. Le tout est recouvert d'une couche de polyimide puis d'ITO.They can also be covered with different layers allowing the production of colored filters; thus, for example, they can be covered with a Cr or NiCr film, which is then etched by photolithography. A tiling of colors (red, green, blue) is then carried out by depositing colors and photolithography. The whole is covered with a layer of polyimide then ITO.
Ils peuvent être recouverts d'une série de couches dont au moins l'une d'entre elles devient luminescente sous l'effet d'une décharge électrique.They can be covered with a series of layers, at least one of which becomes luminescent under the effect of an electric discharge.
Les dalles ainsi obtenues sont associées pour former des écrans de visualisation tels que les écrans à cristaux liquides, à plasma ou électroluminescents.The slabs thus obtained are combined to form display screens such as liquid crystal, plasma or electroluminescent screens.
Les verres selon l'invention permettent d'obtenir des emballages, tels que des flacons ou des biberons, dont l'usage nécessite une bonne résistance aux chocs thermiques et une grande inertie chimique à l'égard des produits qu'ils sont susceptibles de contenir. Ces emballages sont obtenus par la technique bien connue de soufflage ou de pressage d'une paraison dans un moule.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9207778A FR2692883B1 (en) | 1992-06-25 | 1992-06-25 | Thermally stable and chemically resistant glasses. |
| FR9207778 | 1992-06-25 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0576362A2 true EP0576362A2 (en) | 1993-12-29 |
| EP0576362A3 EP0576362A3 (en) | 1994-11-30 |
| EP0576362B1 EP0576362B1 (en) | 1999-08-18 |
Family
ID=9431159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93401624A Expired - Lifetime EP0576362B1 (en) | 1992-06-25 | 1993-06-24 | Thermally stable und chemically resistant glasses |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5506180A (en) |
| EP (1) | EP0576362B1 (en) |
| JP (1) | JP3400018B2 (en) |
| CA (1) | CA2099217C (en) |
| DE (1) | DE69326039T2 (en) |
| ES (1) | ES2137236T3 (en) |
| FI (1) | FI113962B (en) |
| FR (1) | FR2692883B1 (en) |
| TW (1) | TW279154B (en) |
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| US5459109A (en) * | 1994-09-19 | 1995-10-17 | Corning Incorporated | Substrate glasses for plasma displays |
| EP0714862A1 (en) * | 1994-11-30 | 1996-06-05 | Asahi Glass Company Ltd. | Alkali-free glass and flat panel display |
| US6060168A (en) * | 1996-12-17 | 2000-05-09 | Corning Incorporated | Glasses for display panels and photovoltaic devices |
| US6089043A (en) * | 1996-04-05 | 2000-07-18 | Saint-Gobain Vitrage | Method for producing glass sheets using flotation |
| DE10150884A1 (en) * | 2001-10-16 | 2003-05-08 | Schott Glas | Alkali borosilicate glass used in the production of flat glass comprises oxides of silicon, boron, aluminum, sodium and potassium, and optionally calcium |
| EP1528043A2 (en) | 1998-01-26 | 2005-05-04 | Saint-Gobain Glass France | Process and appartus for refining glass by centrifuging |
| FR2886288A1 (en) * | 2005-05-27 | 2006-12-01 | Saint Gobain | Glass substrate with low alkaline oxide content and improved properties for the fabrication of flat screens for plasma display panel and liquid crystal display applications |
| US7833919B2 (en) | 2006-02-10 | 2010-11-16 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8007913B2 (en) | 2006-02-10 | 2011-08-30 | Corning Incorporated | Laminated glass articles and methods of making thereof |
| US8598055B2 (en) | 2008-05-30 | 2013-12-03 | Corning Incorporated | Boroalumino silicate glasses |
| US8713967B2 (en) | 2008-11-21 | 2014-05-06 | Corning Incorporated | Stable glass sheet and method for making same |
| DE102014119594A1 (en) | 2014-12-23 | 2016-06-23 | Schott Ag | Borosilicate glass with low brittleness and high intrinsic strength, its preparation and its use |
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| JP3153710B2 (en) * | 1994-01-21 | 2001-04-09 | ホーヤ株式会社 | Glass for silicon pedestal and silicon substrate type sensor |
| DE19739912C1 (en) * | 1997-09-11 | 1998-12-10 | Schott Glas | New alkali-free aluminoborosilicate glass |
| CN1160268C (en) | 1998-11-30 | 2004-08-04 | 康宁股份有限公司 | Glasses for flat panel displays |
| DE19934072C2 (en) * | 1999-07-23 | 2001-06-13 | Schott Glas | Alkali-free aluminoborosilicate glass, its uses and processes for its manufacture |
| JP2003002729A (en) * | 2001-06-19 | 2003-01-08 | Asahi Glass Co Ltd | Inorganic building material and production method therefor |
| US7038347B2 (en) * | 2004-05-03 | 2006-05-02 | Visteon Global Technologies, Inc. | Optimized alternator bobbin |
| US9782949B2 (en) * | 2008-05-30 | 2017-10-10 | Corning Incorporated | Glass laminated articles and layered articles |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5459109A (en) * | 1994-09-19 | 1995-10-17 | Corning Incorporated | Substrate glasses for plasma displays |
| WO1996009259A1 (en) * | 1994-09-19 | 1996-03-28 | Corning Incorporated | Substrate glasses for plasma displays |
| EP0714862A1 (en) * | 1994-11-30 | 1996-06-05 | Asahi Glass Company Ltd. | Alkali-free glass and flat panel display |
| US6089043A (en) * | 1996-04-05 | 2000-07-18 | Saint-Gobain Vitrage | Method for producing glass sheets using flotation |
| US6060168A (en) * | 1996-12-17 | 2000-05-09 | Corning Incorporated | Glasses for display panels and photovoltaic devices |
| USRE38959E1 (en) * | 1996-12-17 | 2006-01-31 | Corning Incorporated | Glasses for display panels and photovoltaic devices |
| USRE41127E1 (en) * | 1996-12-17 | 2010-02-16 | Corning Incorporated | Glasses for display panels and photovoltaic devices |
| EP1528043A2 (en) | 1998-01-26 | 2005-05-04 | Saint-Gobain Glass France | Process and appartus for refining glass by centrifuging |
| DE10150884A1 (en) * | 2001-10-16 | 2003-05-08 | Schott Glas | Alkali borosilicate glass used in the production of flat glass comprises oxides of silicon, boron, aluminum, sodium and potassium, and optionally calcium |
| FR2886288A1 (en) * | 2005-05-27 | 2006-12-01 | Saint Gobain | Glass substrate with low alkaline oxide content and improved properties for the fabrication of flat screens for plasma display panel and liquid crystal display applications |
| WO2007000540A2 (en) * | 2005-05-27 | 2007-01-04 | Saint-Gobain Glass France | Glass substrates for flat screens |
| WO2007000540A3 (en) * | 2005-05-27 | 2007-08-09 | Saint Gobain | Glass substrates for flat screens |
| US7833919B2 (en) | 2006-02-10 | 2010-11-16 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8007913B2 (en) | 2006-02-10 | 2011-08-30 | Corning Incorporated | Laminated glass articles and methods of making thereof |
| US8753993B2 (en) | 2006-02-10 | 2014-06-17 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8763429B2 (en) | 2006-02-10 | 2014-07-01 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US10364177B2 (en) | 2006-02-10 | 2019-07-30 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8598055B2 (en) | 2008-05-30 | 2013-12-03 | Corning Incorporated | Boroalumino silicate glasses |
| USRE46337E1 (en) | 2008-05-30 | 2017-03-14 | Corning Incorporated | Boroalumino silicate glasses |
| US8713967B2 (en) | 2008-11-21 | 2014-05-06 | Corning Incorporated | Stable glass sheet and method for making same |
| DE102014119594A1 (en) | 2014-12-23 | 2016-06-23 | Schott Ag | Borosilicate glass with low brittleness and high intrinsic strength, its preparation and its use |
| DE102014119594B4 (en) | 2014-12-23 | 2019-02-07 | Schott Ag | Borosilicate glass with low brittleness and high intrinsic strength, its preparation and its use |
| US10442723B2 (en) | 2014-12-23 | 2019-10-15 | Schott Ag | Borosilicate glass with low brittleness and high intrinsic strength, the production thereof, and the use thereof |
| DE102014119594B9 (en) | 2014-12-23 | 2020-06-18 | Schott Ag | Low brittleness and high intrinsic strength borosilicate glass, its manufacture and use |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0576362A3 (en) | 1994-11-30 |
| CA2099217A1 (en) | 1993-12-26 |
| FR2692883B1 (en) | 1994-12-02 |
| JPH0656469A (en) | 1994-03-01 |
| US5506180A (en) | 1996-04-09 |
| FR2692883A1 (en) | 1993-12-31 |
| EP0576362B1 (en) | 1999-08-18 |
| DE69326039D1 (en) | 1999-09-23 |
| ES2137236T3 (en) | 1999-12-16 |
| JP3400018B2 (en) | 2003-04-28 |
| DE69326039T2 (en) | 2000-04-06 |
| FI932930A (en) | 1993-12-26 |
| TW279154B (en) | 1996-06-21 |
| FI932930A0 (en) | 1993-06-24 |
| CA2099217C (en) | 2003-10-28 |
| FI113962B (en) | 2004-07-15 |
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